DE2262780A1 - PROCESS FOR THE MANUFACTURING OF CATIONIC COLORS - Google Patents

Description

Process for the preparation of cationic dyes.

m

The present invention relates to a process for the preparation of cationic dyes in the form of " concentrated aqueous solutions. · 'The production of cationic dyes by

^, Conversion of the corresponding water-insoluble basic dyes into the water-soluble dye salts is carried out by treating the basic dye with alkylating agents. This alkylation is usually carried out in high-boiling

. inert organic, non-polar, immiscible with water " Solvents such as tetrachloroethane or chlorobenzene, 'at

. . Temperatures above 100 ⁰ C carried out. However, this process "has disadvantages, if carried out on a technical scale, because the use of an organic solvent represents an undesirable hazard and an additional step must be carried out to recover the solvent in order to be able to carry out the process economically." Furthermore it is necessary ^ to the

309827/1064

CIBA-GEIGYAG

• *. 2262785 -

Carry out the reaction to the end, usually to heat the solvent to its boiling point, and it must, in order to be able to control the reaction, the solvent and the filter cake must be anhydrous.

However, the use of such high temperatures leads to decomposition reactions in sensitive compounds. To isolate the products, it is suggested, for example, by adding water to the organic solvent transfer the color salts into the aqueous phase. This way of working requires large amounts of water and consequently large-scale apparatus to carry out the phase separation. There are also several extraction operations necessary because the color salts also show a certain solubility in the organic medium. Isolation of the Products obtained by removing organic solvents by means of distillation require high temperatures, so that in turn sensitive dyes are partially decomposed. The same goes for the removal of the for the alkylation hitherto customary solvents by steam distillation. Since long distillation times are required are, the color salts are exposed to a harmful effect of heat for an equally long time. In addition, is complete removal of these organic solvents by steam distillation is difficult.

Also, when quaternizing in an aqueous medium, the use of high temperatures will result in tarry formation

309827/1054

CIBA-GEIGYAG

or oily contaminants result, make it necessary that, in V / ater dissolved product formed by treating mit'einer'Filterhilfe, ■ · · '■ <■' ■ --- \> · how Holzkohlej before isolating the cationic dye

to clean.

Common to all previously known methods * for isolating the end products is that the production of a Storage-stable and ready-to-use concentrated solution. the color salts in a separate operation over the must take place in a fixed form. The present invention makes it possible to avoid these disadvantages.

The present announcement concerns 'now a' Process for the preparation of cationic dyes, -die are free of starting materials or by-products and present in technically and dye-pure form and the formula

Q j

κj ^ _CHCH} .ι

1 ■ · n — 1

(I)

correspond i where R ^ is a methyl, ethyl or propyl group represents, Rp is a hydrogen atom or a of the meanings of the symbol R-, Ϋ has one of the following Formulas $ * ~ ~ "" * "v ~ - - - y

Q or -N = O (- GH = OH ^ M-R «.

309827 / 1Ö54

CtBA-GEIGYAG - ♦ -

corresponds, where B is a hydrogen atom or a low molecular weight alkyl, cyclohexyl, phenyl or benzyl radical means that with cyano, nitro, carbamoyl, hydroxyl, amino or low molecular weight alkoxy groups or with Chlorine or bromine atoms can be substituted, and where D is a phenyl or a 5- or 6-membered heterocyclic Represents ring to which another benzene ring can be fused, the one with chlorine or bromine atoms or substituted with low molecular weight alkyl or alkoxy or phenoxy, nitro or acetylamino groups may be, or which forms a 5- or 6-membered ring with the radical B and the nitrogen atom, and where Q is a Represents a bridge member which, in addition to carbon, can also contain heteroatoms and the Z to form a 5- or 6-membered one Ring supplemented, where Z carry the same substituents as D and contain one or two fused benzene rings can, and in which R is a methyl, ethyl, propyl or benzyl radical and each η and m is 1 or 2 and A ^ is a Represents anion.

The process according to the invention is characterized in that a dye of the formula II

Q,

ι Z,

N = ^ = CH -CH 4 == rc -CR ₀ = N -Y ~ (ll) ni d

in which Y, Q, Z, η and R _{2 have} the meaning given under formula (i), in aqueous, preferably alkaline

309827/1064

CIBA-GEIGYAG

Medium, e.g. in the presence of alkali or alkaline earth oxides,

-acetates /

hydroxides, carbonates, bicarbonates / or mixtures thereof and at temperatures of 5 to 75 C with dimethyl, Diethyl or dipropyl sulfate or with p-toluenesulfonic acid methyl or ethyl ester continuously quaternized, the weight ratio of the dye to. Water in the area holds from 1:30 to 1: 4 and a total of no more as 4 moles of dialkyl sulfoester per mole of dye.

The term "low molecular weight" means that the group in question has 1 to 4, preferably 1 or 2 carbon contains atoms.

-, .., _? ..... ^ 2-s anions come - such · strong »inorganic - ■ -. Acids are possible, for example the "chloride", bromide, iodide, nitrate, sulfate (especially hydrogen sulfate) and phosphate (especially dihydrogen phosphate). Anions of organic acids are also possible, including aryl and alkyl sulfonates and - carbonates are understood., in particular the benzenesulfonate and its _{derivatives substituted with nitro groups, chlorine, bromine s} C, to C ^, - alkyl and C, to C ^ -alkoxy groups, C ₁ to Cj, -Alkylsulfonate ^ anions of aliphatic carboxylic acids with 1 .. to 4 carbon atoms and benzoates in which the benzene ring may have the same substituents as in the benzenesulfonates case of particular importance are the anions 'of niedrigmolekularenj, d _e h "1 to 4 carbon atoms containing Alkylschwefelsäurehalbester Further, the dyes as double ^salts.';

CIBA-GEIGY AQ

with heavy metal halides, especially with Zinc and cadmium halides.

Examples of such anions are; Benzenesulfonate, p-toluenesulfonate, p-methoxybenzenesulfonate, methanesulfonate, Ethanesulfonate, formate, acetate, chloroacetate, propionate, lactate, tartrate, benzoate, methylbenzoate., Methyl sulfate, Ethyl sulfate, ZnCl, "and CdCl,".

Preferably one goes in the invention

Process of dyes of the formula

J

Ο "" Ι

7 ''

ί ^Z ■ ·

i!

N == 4 = CH-CH = ^ == fC-CH = N-N 'or

^ 'n-1 \ i

ί ₇ i IJ 7 H. J

! ί «■! ■

N = ^ CH-CH = $ = -. C-CH = NN = Cf-CH = CH ■■) · ■ _Ί NR,

n-1 'η-1 3

from where Q 'and Q "optionally represent heteroatoms-containing bridge members, the Z ¹ and Z", which may contain further fused-on benzene or naphthalene ring systems, to 5- or 6-membered imidazole, triazole, thiadiazole, thiazole -, Oxazole or pyridine rings, R, a methyl, ethyl or benzyl group ^ B 'a hydrogen atom or a methyl, ethyl, phenyl, benzyl or cyclohexyl group, D' a phenyl or a 5- or 6-membered iieterocyclic ring, where 2 atoms of D 'with the nitrogen atom and 2 or 3 atoms of B' can form a 5 ™ or 6-membered ring, and each m and η

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CIBA-GEIGYAG

Means 1 or 2.

Examples of compounds according to the present invention Invention can be used, are described, for example, in DAS 1 133 054 or DAS 1 038 522.

The basic compounds which can be used according to the present invention are preferably sodium bicarbonate, ' Magnesium oxide, sodium hydroxide, sodium acetate or potassium acetate, or mixtures thereof.

According to the invention, the quaternizing agent is continuously in a total amount of not more than 4 moles of dialkyl sulfoester per mole of dye to one aqueous, preferably c. ± kali'scheri dispersion 'given. "'" "

Depending on the reaction components, the reaction is in a p ^ range to achieve optimal results carried out from 5 to 1 = 2.

The dye concentration in water can vary over a wide range. However, one is preferred Ratio of dye to water in the range from 1:30 to 1: 4.

^: Temperatures from about 5 ° C to about 75 ° C are preferably used in carrying out the process. The preferred temperatures are in the range from about 15 ° C. to about 40 ° C., that is to say that higher temperatures with their disadvantageous effects, for example hydrolysis, are not necessary.

309827/1054

CIBA-GEIGYAG

In general, the process is carried out in such a way that the wet filter cake of the Adding dye to the water. Then the basic compound is preferably added, followed by dropwise Dialkyl sulfate, e.g. at a temperature of 20 to 25 ° C, is added. After the reaction has ended, it is filtered and the cationic dye is isolated by salting out and suction filtration.

It is of course possible to change the order of addition; for example water and dialkyl sulfate be put together first.

.-. ·· .- * '^''Itis' a * advantage of the present process, · that it is not necessary to use solvents and all work related procedures are avoided In addition, the present method is advantageous economically by the desired dye is obtained in good yield. Surprisingly, the quaternization can be carried out not only at a much lower temperature and therefore more gently than before, but also in a much more concentrated solution than is the case when working in the usual organic media. This allows the dyes to be isolated under much gentler conditions. The end products are therefore

■ less contaminated by decomposition products and deliver purer nuances in the coloring. But above all, it offers

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C (BA-GEIGYAG -

the new process is a simple method to produce highly concentrated aqueous solutions in one step Color salts to come. Which can be found directly or after appropriate Dilution as storage-stable liquid 'commercial preparations the dyes in question can be used.

The cationic dyes prepared by the process of the invention can be used for dyeing Materials of various kinds, ζ.B. "of fibers made of polyacrylonitrile or acid-modified polyester or poly-. amide can be used. . ■

In the examples below, the parts mean, unless otherwise stated, parts by weight, the Percentages are percentages by weight, and the temperatures "are in Degrees Celsius indicated, '"■

0 98277105

CIBA-GEIGYAG Example 1.

21.1 parts of the condensation product of pyridine-4-aldehyde and N-methyl-N-phenylhydrazine will be suspended in 350 parts of water. After adding 5.0 parts of magnesium oxide at 30 to 40 ° below Stirring 25 * 2 parts of dimethyl sulfate were added dropwise. One lets Stir for 2 hours and then filter the batch. The dye becomes the from the clear filtrate formula

CH-N. /> - CH = NI— ^ > Cl-

V ¹ V ^

salted out with sodium chloride. The dye colors materials made of polyacrylonitrile in shades of yellow excellent lightfastness.

A dye with equally good properties is obtained if 21.1 parts of the condensation product are used of pyridine-4-aldehyde and N-methyl-N-phenylhydrazine by equivalent amounts of the condensation products of quinoline-2-, acridine-9-, benzthiazol-2-, benzoxp.zol-2-, N-methylbenzimidazole-2, thiazole-2 or oxazole-2-aldehyde with N-phenylhydrazine, N-amino-2,3-dihydroindole, N-amino-carbazole, N-cyclohexyl-N-phenylhydrazine, N-methyl-N-pyridinylhydrazine, N-ethyl-, N-propyl- or N-butyl-

309327/1054

.CIBA-ώ-2'fV-'AS - "

22627.8t) '

N-phenylhydrazine, N-methyl-N- (4 '-chloro-, -bromo-, -methyl-, -phenoxy-, - nitro-, -cyan, 3'-carboxamide-, acetylamino-, 2'-hydroxy- or -tnethoxyphenyl) hydrazine replaced.

309827/1054

CIBA-GEIGY AG

Be i s ρ i e 1 2

19> 7 parts of the condensation product of pyridine-4-aldehyde and phenylhydrazine are suspended in 350 parts of water. After adding 5> O parts of magnesium oxide, At 30 ° to 40 °, 25.2 parts of dimethyl sulfate were added dropwise with stirring. The mixture is left to stir for 2 hours and then the batch is filtered. The clear filtrate becomes the Dye of the formula

Cl

salted out with sodium chloride. The dye colors materials made of polyacrylonitrile in yellow tones.

309827/1054

CIBA-GEIGY AG Example 3

25.7 parts of the condensation product of Pyridine-2-aldehyde and N-amino-1,2,3,4-tetrahydroquinpline are suspended in 350 parts of water. After adding 8.4 parts of sodium bicarbonate are used at 30 to 40 2 parts of dimethyl sulfate were added dropwise with stirring. The mixture is left to stir for 2 hours and the batch is then filtered. The clear filtrate becomes the dye the formula

OH = N-N

salted out with sodium chloride. The dye colors materials made of polyacrylonitrile in shades of yellow excellent lightfastness.

A dye with equally good properties is obtained if 23.7 parts of the condensation product of pyridine-2-aldehyde and N-amino-1,2,3,4-tetrahydroquinoline are replaced by equivalent amounts of the condensation product of N-amino- 1,, 2, 3., 4-tetrahydroquinoline replaced with pyridine, -h- or quinoline-2-j4-aldehydes.

30982-771084

CIBA-GEIGY AQ

- m

Example 4

26.1 parts of the condensation product of quinoline-4-aldehyde and N-methyl-N-phenylhydrazine are suspended in 350 parts of water. At 30 to ^ O, 25.2 parts of dimethyl sulfate are added dropwise with stirring. With simultaneous addition of sodium hydroxide the solution is kept p _u 7-8 discrimination throughout the quaternization. ¹ Man

ri

lets stir for 2 hours and then filtered the batch. The clear filtrate becomes the dye the formula

θ H = N-

salted out with sodium chloride. The dye colors materials made of polyacrylonitrile in shades of yellow excellent lightfastness.

309827/1054

CIBA-GEIGY AG

/ Γ

Example 5

26.2 parts of the condensation product of N-methylquinolone-2-hydrazone and pyridine-4-aldehyde are along with 250 parts of water and 50 parts Dimethyl sulfate heated to 50 to 60 ° with stirring. After 3 hours, excess dimethyl sulfate is decomposed by adding ammonia, and the batch is diluted with 250 parts of water. The dye solution is filtered hot. The clear filtrate becomes the dye of the formula

CH -1

CH = N-N

he

salted out with sodium chloride. The dye colors materials made of polyacrylonitrile in a reddish yellow Shades of good lightfastness. ·

3G9827 / 10S4

CIBA-GEIGY AG Example 6

21.4 parts of the condensation product of N-methylimidazole-2-aldehyde and N-methyl-N-phenylhydrazine are suspended in 350 parts of water. After adding 5> 0 parts of magnesium oxide become at 30 to 40 ° 25.2 parts of dimethyl sulfate were added dropwise with stirring. The mixture is left to stir for 2 hours and then the batch is filtered. The clear filtrate becomes the dye the formula

salted out with sodium chloride. The dye colors materials made of polyacrylonitrile in yellow tones.

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CIBA-GEISYAG

■ Example 7 2262780

26.8 parts of the condensation product of 3-methylbenzthiazolon-2-hydrazone and pyridine-4-aldehyde are suspended in 400 parts of water. After adding 5.0 parts Magnesium oxide becomes at 20 to 40 with stirring. 29.0 Parts of dimethyl sulfate are added dropwise. The mixture is left to stir for 2 hours and the batch is then filtered. From the clear filtrate becomes the color of the formula

CH,

ZnCl ₃

salted out with sodium and zinc chloride. The dye colors materials made of polyacrylonitrile in golden yellow tones of excellent lightfastness.

To an equally good properties having dyestuff is obtained if 26, 8 parts of the condensation product of 3-Methylbenzthiazolon-2-hydrazQn and pyridine A aldehyde ionsprodukt by equivalent amounts of condensation of pyridine-4-aldehyde with N-Methylthiazolon-, - oxazolon- or -benzoxazolon-2-hydrazone, 1,3-dimethylbenzi midazolon ,, /

/ -imidazQlon- or -I, J), 4-triazolon-2-hydrazone _i N-methylpyridone- or -quinolone-4-hydrazonej N-methyl-isoquinolpn-1-hydrazone, 3-ethyl-l, 3, ^ - thiadiazolon ^ -hydrazone or 4-benzyl-1 _J 2 _J 4-thiadiazolon-5-hydrazone replaced.

309827 / 105A

CIBA-GEIGY AQ Example 8

26.8 parts of the condensation product of 3-methylbenzthiazolon-2-hydrazone and pyridine-2-aldehyde diacetate are suspended in 400 parts of water. After adding of 5.0 parts of magnesium oxide are below 20 to 40 Stirring 29.0 parts of dimethyl sulfate were added dropwise. One lets Stir for 2 hours and then filter the batch . The clear filtrate becomes the dye of the formula

CH-

salted out with sodium and zinc chloride. The dye stains Materials made of polyacrylonitrile in golden yellow tones with excellent lightfastness.

309827/1054

Claims (12)

Claims, 1. Process for the production of cationic dyes that are free from starting materials or by-products and are in technically and dye-pure form and of the formula I (D , Corresponding, wherein _R1 is a methyl, ethyl or Prppyl- ' "group is / Rp is a Wasserstoffatöm / or a"' of the meanings of the symbol Y R ₃ has one of the following Formulas -N: Q— or -N = C-f-CH = CH- corresponds to, where B is a hydrogen atom or a low molecular weight alkyl, cyclohexyl ,; ^: -. ". ZS ... ', ..: · Phenyl or benzyl radical means ₃ which can be substituted with cyano, nitro, carbamoyl, hydroxyl, amino or low molecular weight alkoxy groups or with chlorine or bromine atoms, and where D is a phenyl or a 5- or 6-membered heterocyclic ring to which a further benzene ring is fused 30 9827/1054 CIBA-GEIGYAG can, with chlorine or bromine atoms or with low molecular weight alkyl or alkoxy or phenoxy, nitro or acetylamino groups can be substituted, or with the radical B and the nitrogen atom a 5 ~ or 6-membered ring forms, and where Q is a bridge member which, in addition to carbon, also contain heteroatoms can, and the Z complements a 5- or 6-membered ring, where Z carry the same substituents as D and one or may contain two fused benzene rings, and in which R is a methyl, ethyl, propyl or benzyl radical and each m and η is 1 or 2 and A ^ represents an anion, characterized in that a dye of the formula II 1 ' n = 4 = ch-ch4 == c-cr ₂ = ny (ii) wherein Y, Q, Z, η and R are those given under formula (I) Have meaning in an aqueous, preferably alkaline medium and at temperatures from 5 to 75 C with dimethyl, Diethyl or dipropyl sulfate or with p-toluenesulfonic acid methyl or ethyl ester continuously quaternized and a total of not more than 4 moles of dialkyl sulfoester is added per mole of dye. 2. The method according to claim 1, characterized in that that an aqueous dispersion is used that contains alkali or alkaline earth oxides as basic compounds, 309827/1054 CIBA-GEIGYAG ■ w - · ■ hydroxides, carbonates, bicarbonates or acetates or Contains mixtures of the same. 3 · The method according to claim 1, characterized in that the reaction is in a ρ range of
5 to 12 is performed. 4. The method according to claim 1, characterized draws that the reaction is carried out at a temperature of 5 to 75 ° C. 5. The method according to claim 1, characterized in that that the reactants in a molar ratio of "3 to 4 mol of dialkyl sulfoester per mol of hydrazone compound be used. ■ 6. The method according to claim 1, characterized in that that a weight ratio of dye to water / water of 1:30 to 1: 4 is used. 7. The method according to claim 1, characterized in that the dialkyl sulfoester is dimethyl sulfate
is used. \ · 8. The method according to claim 1, characterized in that one of a dye of the formula ! z 1 3Ö9827 / 1054 ^D CIBA-GEIGY AQ emanates from what CH -CH a pyridyl-2- or pyridyl-4-, quinolyl-2- or quinolyl-4-, acridyl-9-, N-methylimidazolyl-2-, N-methylbenzimidazolyl-2-, benzthiazolyl -2-, benzoxazolyl-2-, Is thiazolyl-2- or oxazolyl-2 radical, and B ^{1 is} a hydrogen atom or a methyl, ethyl, phenyl, benzyl or cyclohexyl group and D 'is a phenyl or a 5- or 6-membered heterocyclic ring, where 2 atoms of D ¹ with the nitrogen atom and 2 or 3 atoms of B ^{1 can form} a 5 ^ or 6-membered ring, and η denotes 1 or 2. 9. The method according to claim 8, characterized in that that one starts from a dye of the formula given in claim 8, wherein -W a remainder of the formula 309827/1054 CIBA-GSSGY AG _V S ' -N V ./ or means. . 10. The method according to claim 1, characterized in that one of a dye of the formula Q ¹ "ι No. ¹ -1 ι ι z ¹ n-1 emanating _s wherein f— n-1 has the meanings given in claim 8, and f Z " CH = CH- m-1 309827/1054 C! BA-GcIGY AG a 3-? 4ethyl-benzthiazolinylidene-2-, 3-methyl-thiazolinylidene-2-, 3-iMethyl-benzoxa:; olinylidene-2-, 3-methyloxazolinylidene-2-, 1,3-methylbenzimidazolinylidene-2-, 1, 3 ~ Di ^rr ' ^et hyli ^ra idazolinylidene-2-, 1-methyl-1,2-dihydropyridylidene-2-, 1-methyl-l ^ -dihydropyridylidene ^ l-, l-methyl-l _J 2-dihydroquinolylidene-2- _J 1-methyl-1,4-dihydroquinolylidene-4-j 2-methyl-1,2-dihydroisoquinolylidene-1-, thiadiazolinyliden-2- or 4-benzyl-l, 2 _J represents 4-thiadiazolinyliden-5-rest. 11. The method according to claim 10, characterized in that one starts from a dye of the formula given in claim 10, wherein Q ', Z ¹ and η have the meanings given in claim 10, mi, R is a methyl group and Q "is the ring Z "to the remainder of the formula or added. 12. Use of according to claims 1 to 11 herge-, provided dyes for coloring polyacrylonitrile materials. 309327/1054 original inspected CLBA-GEIGY AG 13- The polyacrylonitrile colored according to claim 12 material. 309327/105Λ